Magnetoresistance effect element

ABSTRACT

A magnetoresistance effect element includes a first ferromagnetic layer, a second ferromagnetic layer, and a tunnel barrier layer that is interposed between the first ferromagnetic layer and the second ferromagnetic layer. The tunnel barrier layer is a stacked body including one or more first oxide layers having a spinel structure and one or more second oxide layers having a spinel structure with a composition which is different from a composition of the first oxide layer.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a continuation of U.S. application Ser. No.17/060,299 filed Oct. 1, 2020, which is a continuation of U.S.application Ser. No. 16/451,791 filed Jun. 25, 2019, which is based onand claims priority under 35 U.S.C. 119 from Japanese Patent ApplicationNo. 2018-123538 filed on Jun. 28, 2018. The contents of the aboveapplications are incorporated herein by reference.

BACKGROUND OF THE INVENTION Field of the Invention

The disclosure relates to a magnetoresistance effect element.

Description of Related Art

A giant magnetoresistance (GMR) element including a multilayered film ofa ferromagnetic layer and a nonmagnetic layer and a tunnelingmagnetoresistance (TMR) element using an insulating layer (a tunnelbarrier layer, a barrier layer) as a nonmagnetic layer are known. Ingeneral, a TMR element has a higher element resistance than a GMRelement, but has a higher magnetoresistance (MR) ratio than a GMRelement. Accordingly, TMR elements have attracted attention as elementsfor a magnetic sensor, a high-frequency component, a magnetic head, anda nonvolatile random-access memory (MRAM).

TMR elements can be classified into two types depending on a differencein a mechanism of tunnel conduction of electrons. One type is TMRelements using only a penetration effect (a tunneling effect) of wavefunctions between ferromagnetic layers. The other type is TMR elementsin which coherent tunneling (in which only electrons having symmetry ofa specific wave function tunnel) using conduction of a specific orbit ofa tunnel barrier layer which is tunneled when a tunneling effect occursis dominant. It is known that a TMR element in which coherent tunnelingis dominant provides a larger MR ratio than a TMR element using only atunneling effect.

MgO is widely known as a material of a tunnel barrier layer in which acoherent tunneling effect is obtained. However, MgO has a large latticemismatch with a ferromagnetic layer and many defects such as dislocationare generated in the tunnel barrier layer of MgO and thus there is aproblem in that a tunneling junction with high quality cannot beobtained. Accordingly, materials substituting MgO have been studied. Forexample, Japanese Patent No. 5586028 discloses a magnetoresistanceeffect element using MgAl₂O₄ having a spinel structure as a materialsubstituting MgO.

Japanese Patent No. 5988019 discloses a magnetoresistance effect elementusing a nonmagnetic oxide having a disordered spinel structure as atunnel barrier layer. According to Japanese Patent No. 5988019, a higherMR ratio is obtained in the disordered spinel structure in a result ofcomparison between a case in which a nonmagnetic oxide having a spinelstructure is used as a tunnel barrier layer (Japanese Patent No.5586028) and a case in which a nonmagnetic oxide having a disorderedspinel structure is used as a tunnel barrier layer.

SUMMARY OF THE INVENTION

A nonmagnetic oxide having a spinel structure has less lattice mismatchwith respect to a ferromagnetic layer, better bias dependency of avoltage, and a higher MR ratio with a high applied voltage in comparisonwith MgO. Accordingly, a nonmagnetic oxide having a spinel structure isexpected to be able to be a material for a tunnel barrier layer of amagnetoresistance effect element for an MRAM which is used with a highapplied voltage. In a magnetoresistance effect element for a memory suchas an MRAM, it is preferable that an output voltage value be higher suchthat accurate reading and writing are possible with a relatively highvoltage. However, since a nonmagnetic oxide having a spinel structurehas a slightly lower MR ratio under a low voltage than MgO, there is aproblem in that it is difficult to enhance an output voltage value.

The disclosure is made in consideration of the above-mentionedcircumstances and an objective thereof is to provide a magnetoresistanceeffect element with a high output voltage value.

The inventors have conducted studies to solve the above-mentionedproblems and thus found that it is possible to enhance an output voltagevalue of a magnetoresistance effect element by forming a tunnel barrierlayer as a stacked body including one or more first oxide layers havinga spinel structure and one or more second oxide layers having a spinelstructure with a composition which is different from a composition ofthe first oxide layer.

That is, the disclosure provides the following means to solve theabove-mentioned problems.

(1) According to an aspect of the disclosure, a magnetoresistance effectelement is provided, including: a first ferromagnetic layer; a secondferromagnetic layer; and a tunnel barrier layer that is interposedbetween the first ferromagnetic layer and the second ferromagneticlayer, wherein the tunnel barrier layer is a stacked body including oneor more first oxide layers having a spinel structure and one or moresecond oxide layers having a spinel structure with a composition whichis different from a composition of the first oxide layer.

(2) In the magnetoresistance effect element according to the aspect,

the first oxide layer may include an oxide containing a metal or analloy which is expressed by General Formula (I)

A_(1-x)B_(x)  (I)

the second oxide layer may include an oxide containing a metal or analloy which is expressed by General Formula (II),

A_(1-y)B_(y)  (II), and wherein,

in General Formula (I) and General Formula (II),

-   -   A's are independently Mg or Zn,    -   B's are independently at least one type of metal selected from        the group consisting of Al, Ga, and In, and    -   x and y satisfy 0<x≤1, 0<y≤1, and |y−x|≥00.005.

(3) In the magnetoresistance effect element according to the aspect, xmay satisfy 0<x<0.5 and y may satisfy 0.5<y≤1, or x may satisfy 0.5<x≤1and y may satisfy 0<y<0.5.

(4) In the magnetoresistance effect element according to the aspect, xmay satisfy 0<x<0.5 and y may satisfy 0.5<y≤1.

(5) In the magnetoresistance effect element according to the aspect, thefirst ferromagnetic layer may be formed on a substrate, the first oxidelayer may be stacked on a surface of the first ferromagnetic layeropposite to the substrate, and the second oxide layer may be stacked ona surface of the first oxide layer opposite to the first ferromagneticlayer.

(6) In the magnetoresistance effect element according to the aspect, thetunnel barrier layer may be a stacked body which includes two firstoxide layers and in which the second oxide layer is interposed betweenthe two first oxide layers.

(7) In the magnetoresistance effect element according to the aspect, athickness of the first oxide layer may be thinner than a thickness ofthe second oxide layer.

(8) In the magnetoresistance effect element according to the aspect, athickness of the tunnel barrier layer may be equal to or less than 3 nm.

(9) In the magnetoresistance effect element according to the aspect, thefirst oxide layer and the second oxide layer may have a disorderedspinel structure.

According to the disclosure, it is possible to provide amagnetoresistance effect element with a high output voltage value.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a sectional view schematically illustrating amagnetoresistance effect element according to a first embodiment of thedisclosure;

FIG. 2 is a diagram illustrating a crystal structure of a spinelstructure;

FIG. 3 is a diagram illustrating a crystal structure of a disorderedspinel structure;

FIG. 4 is a sectional view schematically illustrating amagnetoresistance effect element according to a second embodiment of thedisclosure; and

FIG. 5 is a plan view schematically illustrating a magnetoresistanceeffect device which is used to measure output voltage values ofmagnetoresistance effect elements manufactured in examples when seen ina stacking direction.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, the disclosure will be described in detail with referenceto the accompanying drawings. In the drawings used for the followingdescription, feature parts may be enlarged for the purpose ofconvenience and dimensional ratios of elements or the like may bedifferent from actual values. Materials, dimensions, and the like whichare described in the following description are examples, and thedisclosure is not limited thereto and can be appropriately modifiedwithout departing from the gist of the disclosure.

First Embodiment

FIG. 1 is a sectional view schematically illustrating amagnetoresistance effect element according to a first embodiment of thedisclosure. The magnetoresistance effect element 10 illustrated in FIG.1 includes a substrate 1, a first ferromagnetic layer 2, a secondferromagnetic layer 3, and a tunnel barrier layer 4. Themagnetoresistance effect element 10 may include a cap layer and a bufferlayer in addition to the above-mentioned layers.

Substrate

It is preferable that the substrate 1 have excellent flatness. Forexample, MgO, Si, or AlTiC can be used as the material of the substrate1.

First Ferromagnetic Layer and Second Ferromagnetic Layer

The first ferromagnetic layer 2 and the second ferromagnetic layer 3have magnetization. The magnetoresistance effect element 10 outputs achange in relative angle of the magnetization as a change in resistancevalue. For example, when a magnetization direction of the secondferromagnetic layer 3 is fixed and a magnetization direction of thefirst ferromagnetic layer 2 is set to be variable with respect to themagnetization direction of the second ferromagnetic layer 3, themagnetization direction of the first ferromagnetic layer 2 changes andthus the resistance value of the magnetoresistance effect element 10changes. A layer in which a magnetization direction is fixed isgenerally referred to as a fixed layer, and a layer in which amagnetization direction is variable is generally referred to as a freelayer. Since the change in resistance value is caused according to achange in relative angle of magnetization, a configuration in which noneof the magnetization of the first ferromagnetic layer 2 and the secondferromagnetic layer 3 is fixed may be employed.

The first ferromagnetic layer 2 and the second ferromagnetic layer 3include a ferromagnetic material. Examples of the ferromagnetic materialinclude a metal which is selected from the group consisting of Cr, Mn,Co, Fe, and Ni, an alloy including one or more kinds of metal which areselected from this group, and an alloy including one or more metalsselected from this group and one or more kinds of element from B, C, andN. Particularly, Fe or a CoFe alloy has high spin polarizability and canincrease an MR ratio of the magnetoresistance effect element 10 when itis used for the first ferromagnetic layer 2 or the second ferromagneticlayer 3. Examples of the first ferromagnetic layer 2 and the secondferromagnetic layer 3 include Co—Fe, Co—Fe—B, and Ni—Fe. When the firstferromagnetic layer 2 and the second ferromagnetic layer 3 are in-planemagnetized films, for example, a Co—Ho alloy (CoHo₂) or an Sm—Fe alloy(SmFe₁₂) can be preferably used.

The first ferromagnetic layer 2 and the second ferromagnetic layer 3 maybe formed of a Heusler alloy such as Co₂FeSi. A Heusler alloy has highspin polarizability and can realize a high MR ratio. A Heusler alloycontains an intermetallic compound having a chemical composition of XYZor X₂YZ. Here, X is a transition metal element or a noble metal elementin the Co, Fe, Ni, or Cu group. Y is a transition metal in the Mn, V,Cr, or Ti group or the same elements as X. Z is a typical element inGroups III to V. For example, Co₂FeSi, Co₂FeGe, Co₂FeGa, Co₂MnSi,Co₂Mn_(1-a)Fe_(a)Al_(b)Si_(1-b), or Co₂FeGe_(1-c)Ga_(c) can be used asthe Heusler alloy. The Heusler alloy has high spin polarizability andcan increase the MR ratio of the magnetoresistance effect element 10.

When the magnetization directions of the first ferromagnetic layer 2 andthe second ferromagnetic layer 3 are set to be perpendicular to thestacked surface, it is preferable that the thickness be equal to or lessthan 3 nm. Perpendicular magnetic anisotropy is applied to the firstferromagnetic layer 2 and the second ferromagnetic layer 3 at aninterface with the tunnel barrier layer 4. Since the effect ofperpendicular magnetic anisotropy is attenuated by increasing thethicknesses of the first ferromagnetic layer 2 and the secondferromagnetic layer 3, it is preferable that the thicknesses of thefirst ferromagnetic layer 2 and the second ferromagnetic layer 3 besmall.

When the first ferromagnetic layer 2 is formed as a fixed layer and thesecond ferromagnetic layer 3 is formed as a free layer, a coercive forceof the first ferromagnetic layer 2 is set to be greater than a coerciveforce of the second ferromagnetic layer 3. A difference in coerciveforce can be adjusted using materials constituting the ferromagneticlayers, layers adjacent to the ferromagnetic layers, or the like. Forexample, a material having a greater coercive force than a materialconstituting the second ferromagnetic layer 3 may be used for the firstferromagnetic layer 2 or an antiferromagnetic material such as IrMn orPtMn may be made to be adjacent to the first ferromagnetic layer 2. Inorder to prevent a magnetic field leaking from the first ferromagneticlayer 2 from affecting the second ferromagnetic layer 3, a combinedferromagnetic coupling structure may be employed.

Tunnel Barrier Layer

The tunnel barrier layer 4 is formed as a stacked body including a firstoxide layer 4 a and a second oxide layer 4 b which is stacked on thesurface (the top surface in FIG. 1) of the first oxide layer 4 aopposite to the first ferromagnetic layer 2. The first oxide layer 4 aand the second oxide layer 4 b have a spinel structure. A nonmagneticoxide having a spinel structure generally includes two kinds of metallicelements including element A and element B and is expressed by acomposition formula AB₂O₄. The spinel structure of the first oxide layer4 a and the second oxide layer 4 b is not limited to a regular spinelstructure and also includes a disordered spinel structure.

FIG. 2 is a diagram schematically illustrating a crystal structure of aregular spinel structure. In the regular spinel structure, asillustrated in FIG. 2, a site which element A enters (A site) and a sitewhich element B enters (B site) are fixed and an arrangement of theseelements is regular.

On the other hand, FIG. 3 is a diagram schematically illustrating acrystal structure of a disordered spinel structure. In the disorderedspinel structure, element A or element B can be present in any of a site(site A) coordinating tetrahedrally with oxygen and a site (site B)coordinately octahedrally with oxygen which are illustrated in FIG. 3.The site which element A or element B enters is randomly determined.When element A and element B having different atom radii enter thesites, the crystal structure becomes irregular. A lattice constant (a/2)of a disordered spinel structure is substantially a half of a latticeconstant (a) of a regular spinel structure.

The first oxide layer 4 a and the second oxide layer 4 b have differentcompositions. The different compositions include the following threecases. The first case is a case in which the kinds of metal elementswhich are included in the first oxide layer 4 a and the second oxidelayer 4 b are the same and content proportions of the metal elements aredifferent from each other. The second case is a case in which thecontent proportions of metal elements which are included in the firstoxide layer 4 a and the second oxide layer 4 b are the same and thekinds of the metal elements are different from each other. The thirdcase is a case in which both the kinds and the content proportions ofmetal elements which are included in the first oxide layer 4 a and thesecond oxide layer 4 b are different from each other. In themagnetoresistance effect element 10 according to this embodiment, sincethe tunnel barrier layer 4 is formed as a stacked body including one ormore layers of the first oxide layer 4 a and one or more layers of thesecond oxide layer 4 b, which have different compositions, an outputvoltage value is improved. The reason therefor has not been fullyelucidated but is thought to be as follows.

An output voltage value V_(output) of the magnetoresistance effectelement 10 is a maximum value of values which are calculated usingEquation (1).

$\begin{matrix}{{V_{output}(V)} = {\frac{1}{2}V_{Bias}\frac{{TMR}(V)}{1 + {{TMR}(V)}}}} & (1)\end{matrix}$

In Equation (1), V_(Bias) is a bias voltage which is applied to themagnetoresistance effect element 10.

TMR(V) denotes an MR ratio when a bias voltage is applied to themagnetoresistance effect element 10. An MR ratio decreases as theapplied bias voltage increases.

The maximum value of the output voltage value V_(output) can becalculated by measuring the MR ratio while changing the bias voltagevalue V_(Bias).

In order to increase the output voltage value V_(output) of themagnetoresistance effect element 10, it is effective to increase the MRratio and the bias voltage value V_(half). V_(half) is a voltage whenthe MR ratio at the time of application of the bias voltage is half theMR ratio at the time of application of a low bias and is an indicator ofthe quantity of decrease in MR ratio.

The MR ratio and V_(half) of the magnetoresistance effect element 10vary greatly depending on the composition of the tunnel barrier layer 4.In general, the tunnel barrier layer 4 (for example, MgO) having acomposition which is effective for improvement in MR ratio is likely tobe less effective in improving V_(half), and the tunnel barrier layer 4(for example, spinel) having a composition which is effective forimprovement in V_(half) is likely to be less effective in improving theMR ratio. In the magnetoresistance effect element 10 according to thisembodiment, by forming the tunnel barrier layer 4 as a stacked bodyincluding an oxide film having a composition which is effective forimprovement in MR ratio and an oxide film having a composition which iseffective for improvement in V_(half), it is possible to improve the MRratio and V_(half) with good balance. Accordingly, the output voltagevalue in the magnetoresistance effect element 10 according to thisembodiment is improved.

The first oxide layer 4 a includes an oxide containing a metal or analloy which is expressed by General Formula (I), and the second oxidelayer 4 b includes an oxide containing a metal or an alloy which isexpressed by General Formula (II).

A_(1-x)B_(x)  (I)

A_(1-y)B_(y)  (II),

Here, in General Formula (I) and General Formula (II), A's areindependently Mg or Zn, B's are independently at least one type of metalselected from the group consisting of Al, Ga, and In, and x and ysatisfy 0<x≤1, 0<y≤1, and |y−x|≥0.005. When x or y is 1, it ispreferable that element B be Al. The first oxide layer 4 a or the secondoxide layer 4 b which is formed of an oxide of Al is a γ-alumina layerand is preferably an oxide layer having a disordered spinel structure inwhich Al randomly enters A sites and B sites.

By setting the relationship between x and y to |y−x|≥0.005, it ispossible to form one of the first oxide layer 4 a and the second oxidelayer 4 b as an oxide film having a composition which is effective forimprovement in MR ratio and to form the other as an oxide film having acomposition which is effective for improvement in V_(half) When |y−x| isexcessively large, there is concern that lattice matching of the firstoxide layer 4 a and the second oxide layer 4 b will decrease.Accordingly, it is preferable that x and y satisfy |y−x|≤0.8. When|y−x|0.005 is satisfied, the kinds of element A and element B which areincluded in the first oxide layer 4 a and the second oxide layer 4 b,respectively, may be the same as or different from each other.

It is preferable that x satisfy 0<x<0.5 and y satisfy 0.5<y≤1 or that xsatisfy 0.5<x≤1 and y satisfy 0<y<0.5. That is, it is preferable thatone of the first oxide layer 4 a and the second oxide layer 4 b containmore element A than element B and the other contain more element B thanelement A. In this case, the difference in composition between the firstoxide layer 4 a and the second oxide layer 4 b increases and the outputvoltage value is more reliably improved. In general, an oxide layercontaining more element A than element B is effective for improvement inMR ratio. On the other hand, an oxide layer containing more element Bthan element A is effective for improvement in V_(half).

An oxide layer containing more element A than element B is generallylikely to have higher crystallinity than an oxide layer containing moreelement B than element A. Accordingly, it is preferable that an oxidelayer containing more element A than element B be disposed on thesubstrate 1 side. That is, in the magnetoresistance effect element 10according to this embodiment, it is preferable that the first oxidelayer 4 a be formed as an oxide layer containing more element A thanelement B and the second oxide layer 4 b be formed as an oxide layercontaining more element B than element A. By improving crystallinity ofthe first oxide layer 4 a, it is possible to improve lattice matchingbetween the first ferromagnetic layer 2 and the first oxide layer 4 a.When the magnetoresistance effect element 10 is manufactured, the firstferromagnetic layer 2, the first oxide layer 4 a, the second oxide layer4 b, and the second ferromagnetic layer 3 are sequentially stacked inthis order from the substrate 1. Accordingly, by forming the first oxidelayer 4 a which is first stacked as an oxide layer containing moreelement A having high crystallinity than element B, it is possible toimprove crystallinity of the second oxide layer 4 b which is stackedlater.

When the first oxide layer 4 a is formed as an oxide layer containingmore element A than element B, it is preferable that the thickness ofthe first oxide layer 4 a be less than the thickness of the second oxidelayer 4 b. Specifically, it is preferable that the thickness of thefirst oxide layer 4 a be equal to or less than 1 nm. By decreasing thethickness of the first oxide layer 4 a, it is possible to furtherimprove crystallinity of the first oxide layer 4 a.

It is preferable that the thickness of the tunnel barrier layer 4 beequal to or less than 3 nm. When the thickness of the tunnel barrierlayer 4 is equal to or less than 3 nm, wave functions of the firstferromagnetic layer 2 and the second ferromagnetic layer 3 are likely tooverlap over the tunnel barrier layer 4 and a tunneling effect and acoherent tunneling effect of the wave functions between theferromagnetic layers are more easily obtained.

Shape and Dimensions of Element

The stacked body including the first ferromagnetic layer 2, the tunnelbarrier layer 4, and the second ferromagnetic layer 3 which constitutethe magnetoresistance effect element 10 has a pillar shape. The shape ofthe stacked body in plan view can have various shapes such as a circle,a tetragon, a triangle, and a polygon and is preferably a circle in viewof symmetry. That is, the stacked body preferably has a columnar shape.

When the stacked body has a columnar shape, the diameter thereof in planview is preferably equal to or less than 80 nm, more preferably equal toor less than 60 nm, and still more preferably equal to or less than 30nm. When the diameter is equal to or less than 80 nm, a domain structureis not likely to be formed in the ferromagnetic layers, and it is notnecessary to consider a component which is different from spinpolarization in the ferromagnetic metal layers. In the case where thediameter is 30 nm or less, a single domain structure is formed in theferromagnetic layers, and a speed or a probability of a magnetizationreversal is improved. When the diameter is equal to or less than 30 nm,a single domain structure is formed in the ferromagnetic layer and amagnetization switching speed or probability is improved. In aminiaturized magnetoresistance effect element, there is strong demandfor a decrease in resistance.

Method of Manufacturing Magnetoresistance Effect Element

A method of manufacturing a magnetoresistance effect element will bedescribed below.

The method of manufacturing a magnetoresistance effect element accordingto this embodiment includes a step of stacking the first ferromagneticlayer, the tunnel barrier layer, and the second ferromagnetic layer.Known methods such as a sputtering method, a vapor deposition method, alaser ablation method, and a molecular beam epitaxial (MBE) method canbe used as the method of forming the layers.

The tunnel barrier layer is formed by first stacking the first oxidelayer and then stacking a second oxide layer thereon. The first oxidelayer and the second oxide layer can be formed using a method includinga step of forming a metal film, a step of oxidizing the formed metalfilm to acquire an oxide film, and performing a heat treatment on theoxide film.

Known methods such as a sputtering method, a vapor deposition method, alaser ablation method, and a molecular beam epitaxial (MBE) method canbe used as the method of forming the metal film. For example, the firstoxide layer can be formed using a method of performing sputtering usinga target containing a metal or alloy which is expressed by GeneralFormula (I). The second oxide layer can be formed using a method ofperforming sputtering using a target containing a metal or alloy whichis expressed by General Formula (II).

A plasma oxidation method or a natural oxidation method based onintroduction of oxygen can be used as the method of oxidizing the metalfilm. The heat treatment of the oxide film varies depending on acomposition of the oxide and is preferably performed in a vacuum at atemperature range of 350° C. or more and 500° C. or less in general.

The method of forming the tunnel barrier layer is not limited to theabove-mentioned method. For example, the metal film may be formed usinga method of performing co-sputtering using a target containing element Aand a target containing element B. The oxide film may be directly formedusing a target of an oxide containing element A and element B.Alternatively, the oxide film may be formed while oxidizing the metalfilm using a reactive film formation method.

As described above, in the magnetoresistance effect element 10 accordingto the first embodiment, the tunnel barrier layer 4 is formed as astacked body including one first oxide layer 4 a having a spinelstructure and one second oxide layer 4 b having a spinel structure witha composition which is different from a composition of the first oxidelayer. Accordingly, by forming one of the first oxide layer 4 a and thesecond oxide layer 4 b as an oxide film having a composition which iseffective for improvement in MR ratio and forming the other as an oxidefilm having a composition which is effective for improvement inV_(half), it is possible to improve the MR ratio and V_(half) of themagnetoresistance effect element 10 with good balance and thus toimprove the output voltage value.

Second Embodiment

FIG. 4 is a sectional view schematically illustrating amagnetoresistance effect element according to a second embodiment of thedisclosure. In the magnetoresistance effect element 20 according to thesecond embodiment, the same elements as in the magnetoresistance effectelement 10 according to the first embodiment will be referred to by thesame reference signs and description thereof will not be repeated.

In the magnetoresistance effect element 20 illustrated in FIG. 4, atunnel barrier layer 24 is a stacked body which includes two first oxidelayers 4 a and in which a second oxide layer 4 b is interposed betweenthe two first oxide layers 4 a. The first oxide layer 4 a containselement A and element B at an atomic ratio (element A:element B) of1-x:x (0<x≤1) and the second oxide layer 4 b contains element A andelement B at an atomic ratio (element A:element B) of 1−y:y (0<y≤1),where x and y satisfy |y−x|≥0.005. That is, the two first oxide layers 4a are oxide layers containing more element A in comparison with thesecond oxide layer 4 b and thus have higher crystallinity. Thecompositions of the two first oxide layers 4 a may be the same as ordifferent from each other. For example, the proportions of element A andelement B in the two first oxide layers 4 a may be different from eachother and the kinds of element A and/or element B therein may bedifferent.

Since the first oxide layer 4 a has higher crystallinity than the secondoxide layer 4 b, lattice matching between the first ferromagnetic layer2 and the first oxide layer 4 a and between the first oxide layer 4 aand the second ferromagnetic layer 3 is improved. By interposing thesecond oxide layer 4 b between the first oxide layers 4 a having highcrystallinity, the crystallinity of the second oxide layer 4 b isimproved.

Since the magnetoresistance effect element 20 includes two first oxidelayers 4 a, the thickness per layer can be decreased. It is preferablethat the thickness of one layer of the first oxide layers 4 a be equalto or less than 0.5 nm. In this case, the crystallinity of the firstoxide layer 4 a is further improved.

Others

The magnetoresistance effect element 10 may have one of a top pinstructure in which a magnetization-fixed layer is disposed farther froma substrate than a magnetization-free layer and a bottom pin structurein which a magnetization-fixed layer is disposed closer to a substratethan a magnetization-free layer.

The tunnel barrier layer 4 in the magnetoresistance effect element 10according to the first embodiment is formed as a stacked body of onefirst oxide layer 4 a and one second oxide layer 4 b, and the tunnelbarrier layer 24 in the magnetoresistance effect element 20 according tothe second embodiment is formed as a stacked body of two first oxidelayers 4 a and one second oxide layer 4 b. The numbers of the firstoxide layers 4 a and the second oxide layers 4 b are not particularlylimited as long as one or more layers thereof are included. For example,the number of first oxide layers 4 a may be three and the number ofsecond oxide layers 4 b may be two. It is preferable that an oxide layerhaving higher crystallinity be disposed to be in contact with the firstferromagnetic layer 2 and the second ferromagnetic layer 3. It ispreferable that the thickness of the tunnel barrier layer as a whole beequal to or less than 3 nm.

The tunnel barrier layer 4 or 24 may include a third oxide layer havinga composition which is different from those of the first oxide layer 4 aand the second oxide layer 4 b. In this case, it is preferable that thethird oxide layer have an intermediate composition between that of thefirst oxide layer 4 a and that of the second oxide layer 4 b and beinterposed between the first oxide layer and the second oxide layer.

As described above, the magnetoresistance effect elements according tothe embodiments can be effectively used as a memory such as an MRAM.

EXAMPLES Examples 1 to 30 and Comparative Examples 1 to 19

The magnetoresistance effect element 10 illustrated in FIG. 1 wasmanufactured. First, a MgO (001) single-crystal substrate was preparedas a substrate 1, a Cr layer with a thickness of 40 nm was formed as abuffer layer (also serving as a first wire 31 which will be describedlater) on the substrate 1, and an Fe layer with a thickness of 30 nm wasstacked as the first ferromagnetic layer 2 thereon.

Then, an Mg_(1-x)Al_(x) alloy film which is expressed by a generalformula Mg_(1-x)Al_(x) (where x has a value described in Table 1A andTable 1B) was formed in a thickness of 0.8 nm on the first ferromagneticlayer 2 using a sputtering method. Subsequently, the alloy film wasoxidized to form an oxide film and a heat treatment was performedthereon to form a first oxide layer 4 a. The oxidization process wasperformed by exposing the alloy film to the air under a pressure of 5 Pafor 600 seconds. The heat treatment was performed by heating the oxidefilm in a vacuum at 400° C. for 15 minutes. Subsequently, anMg_(1-y)Al_(y) alloy film which is expressed by a general formulaMg_(1-y)Al_(y) (where y has a value described in Table 1A and Table 1B)was formed in a thickness of 0.8 nm on the first oxide layer 4 a using asputtering method, the alloy film was oxidized to form an oxide film,and a heat treatment was performed thereon to form a second oxide layer4 b. The conditions of the oxidization process and the heat treatmentwere set to be the same as in the first oxide layer 4 a. In this way, atunnel barrier layer 4 which is a stacked body including the first oxidelayer 4 a and the second oxide layer 4 b was stacked on the firstferromagnetic layer 2.

Then, an Fe layer was stacked in a thickness 6 nm as a secondferromagnetic layer 3 on the tunnel barrier layer 4 to obtain aferromagnetic tunnel junction. An IrMn layer was formed in a thicknessof 12 nm as an antiferromagnetic layer on the second ferromagnetic layer3, and an Ru layer was formed in a thickness of 20 nm as a cap layer(also serving as a second wire 32 which will be described later) thereonto obtain a magnetoresistance effect element 10. Finally, the resultantwas heated at a temperature of 175° C. while applying a magnetic fieldof 5 kOe thereto, whereby uniaxial magnetic anisotropy was given to thesecond ferromagnetic layer 3.

As described above, the magnetoresistance effect element 10 in which thetunnel barrier layer 4 is a stacked body including the first oxide layer4 a and the second oxide layer 4 b having the compositions which aredescribed in Table 1A and Table 1B was manufactured.

In the manufactured magnetoresistance effect element 10, contentproportions (atomic ratios) of Mg and Al in the first oxide layer 4 aand the second oxide layer 4 b of the tunnel barrier layer were measuredas follows. As a result, it was ascertained that the content proportionsof Mg and Al in the first oxide layer 4 a were almost the same as thatin the Mg_(1-x)Al_(x) alloy film and the content proportions of Mg andAl in the second oxide layer 4 b were almost the same as that in theMg_(1-y)Al_(y) alloy film.

Method of Measuring Content Proportions of Mg and Al

The magnetoresistance effect element 10 was cut along a plane parallelto the stacking direction thereof using a focused ion beam tomanufacture thin sample pieces of the tunnel barrier layer. Thecomposition of the thin sample pieces was analyzed by energy-dispersiveX-ray analysis (EDS) in a transmission electron microscope (TEM). Theanalysis method is not limited thereto, and a secondary ion massspectroscopy (SIMS), an atom probe method, or an electron energy lossspectroscopy (EELS) may be used.

The crystal structure of the tunnel barrier layer 4 in the manufacturedmagnetoresistance effect element 10 was ascertained by section TEMobservation. As a result, it was ascertained that both the oxide of theMg_(1-x)Al_(x) alloy film in which x was in the range of 0.25 to 1.00and the oxide of the Mg_(1-y)Al_(y) in which y was in the range of 0.25to 1.00 had a disordered spinel structure. On the other hand, it wasascertained that both the oxide of the Mg film in which x was 0.00 andthe oxide of the Mg film in which y was 0.00 had a rock salt structureand were MgO.

An output voltage value V_(output) of the manufactured magnetoresistanceeffect element 10 was measured as follows. The results are described inTable 1A and Table 1B.

Method of Measuring Output Voltage Value

FIG. 5 is a plan view schematically illustrating a magnetoresistanceeffect device 30 which is used to measure the output voltage value whenseen in the stacking direction. The magnetoresistance effect element 10was disposed at a position at which a first wire 31 and a second wire 32intersect each other. The magnetoresistance effect element 10 was formedin a columnar shape with a diameter of 80 nm. An electrode 33 wasprovided in the first wire 31, and the electrode 33 was connected to apower supply 34 and a voltmeter 35. By applying a voltage using thepower supply 34, a current flows in the stacking direction of themagnetoresistance effect element 10. Potential differences of themagnetoresistance effect elements 10 and 20 were monitored by thevoltmeter 35.

Change in resistance value of the magnetoresistance effect element 10was observed by applying a bias voltage to the magnetoresistance effectelement 10 of the magnetoresistance effect device 30 while scanning themagnetoresistance effect element with a magnetic field from the outside,and TMR(V) was calculated from the change in resistance value. TMR(V)was calculated using Equation (2).

TMR(V)=(R_(AP)(V)−R_(P)(V))/R_(P)(V)×100  (2)

In Equation (2), R_(P)(V) denotes resistance when the magnetizationdirections of the first ferromagnetic layer 2 and the secondferromagnetic layer 3 are parallel to each other at the time ofapplication of the bias voltage. R_(AP)(V) denotes resistance when themagnetization directions of the first ferromagnetic layer 2 and thesecond ferromagnetic layer 3 are antiparallel to each other at the timeof application of the bias voltage.

The output voltage value V_(output) was measured as follows.

A bias voltage value V_(Bias) was applied to the magnetoresistanceeffect element 10 of the magnetoresistance effect device 30 and TMR(V)was measured. Then, the bias voltage value V_(Bias) and the acquiredvalue of TMR(V) were substituted into Equation (1) to calculate theoutput voltage value V_(output). The maximum value of the calculatedvalues is described as the output voltage value in Table 1A and Table1B.

TABLE 1A Output First oxide layer Second oxide layer voltage x ofMg_(1−x)Al_(x) y of Mg_(1−y)Al_(y) value alloy alloy |y − x| (V)Comparative 0.00 0.00 0.00 0.18 Example 1 Comparative 0.25 0.25 0.19Example 2 Comparative 0.33 0.33 0.20 Example 3 Comparative 0.50 0.500.20 Example 4 Comparative 0.67 0.67 0.21 Example 5 Comparative 0.750.75 0.21 Example 6 Comparative 1.00 1.00 0.21 Example 7 Comparative0.25 0.00 0.25 0.19 Example 8 Comparative 0.25 0.00 0.20 Example 9Example 1 0.33 0.08 0.30 Example 2 0.50 0.25 0.30 Example 3 0.67 0.420.34 Example 4 0.75 0.50 0.34 Example 5 1.00 0.75 0.34 Comparative 0.330.00 0.33 0.20 Example 10 Example 6 0.25 0.08 0.30 Comparative 0.33 0.000.28 Example 11 Example 7 0.50 0.17 0.30 Example 8 0.67 0.34 0.34Example 9 0.75 0.42 0.34 Example 10 1.00 0.67 0.34 Comparative 0.50 0.000.50 0.20 Example 12 Example 11 0.25 0.25 0.30 Example 12 0.33 0.17 0.30Comparative 0.50 0.00 0.28 Example 13 Example 13 0.67 0.17 0.30 Example14 0.75 0.25 0.30 Example 15 1.00 0.50 0.30

TABLE 1B Output First oxide layer Second oxide layer voltage x ofMg_(1−x)Al_(x) y of Mg_(1−y)Al_(y) value alloy alloy |y − x| (V)Comparative 0.67 0.00 0.67 0.21 Example 14 Example 16 0.25 0.42 0.33Example 17 0.33 0.34 0.33 Example 18 0.50 0.17 0.30 Comparative 0.670.00 0.28 Example 15 Example 19 0.75 0.08 0.30 Example 20 1.00 0.33 0.30Comparative 0.75 0.00 0.75 0.21 Example 16 Example 21 0.25 0.50 0.33Example 22 0.33 0.42 0.33 Example 23 0.50 0.25 0.30 Example 24 0.67 0.080.30 Comparative 0.75 0.00 0.28 Example 17 Example 25 1.00 0.25 0.30Comparative 1.00 0.00 1.00 0.20 Example 18 Example 26 0.25 0.75 0.33Example 27 0.33 0.67 0.33 Example 28 0.50 0.50 0.30 Example 29 0.67 0.330.30 Example 30 0.75 0.25 0.30 Comparative 1.00 0.00 0.24 Example 19

From the results described in Table 1A and Table 1B, it was ascertainedthat the magnetoresistance effect elements of Examples 1 to 30 in whichthe tunnel barrier layer 4 which was a stacked body of the first oxidelayer 4 a and the second oxide layer 4 b having disordered spinelstructures with different compositions had an output voltage valuehigher than those of the magnetoresistance effect elements ofComparative Examples 1 to 19. The reason why the output voltage valuesof the magnetoresistance effect elements of Comparative Examples 1 to 8,10, 12, 14, 16, and 18 were low is thought to be that the first oxidelayer 4 a or the second oxide layer 4 b was an MgO layer. The reason whyoutput voltage values of the magnetoresistance effect elements ofComparative Examples 9, 11, 13, 15, 17, and 19 were low is thought to bethat the first oxide layer 4 a and the second oxide layer 4 b had thesame composition.

Particularly, the output voltage values of the magnetoresistance effectelements of Examples 3 to 5, 8 to 10, 16 to 17, 21 to 22, and 26 to 27were in the range of 0.33 V to 0.34 V, which is high. The reason why theoutput voltage values of the magnetoresistance effect elements ofExamples 3 to 5 and 8 to 10 were high is thought to be that x of thefirst oxide layer 4 a satisfied 0<x<0.5 and y of the second oxide layer4 b satisfied 0.5<y≤1. The reason why the output voltage values of themagnetoresistance effect elements of Examples 16 to 17, 21 to 22, and 26to 27 were high is thought to be that x of the first oxide layer 4 asatisfied 0.5<x≤1 and y of the second oxide layer 4 b satisfied 0<y<0.5.

In Examples 4 to 5 and 9 to 10 in which x of the first oxide layer 4 astacked on the surface of the first ferromagnetic layer 2 opposite tothe substrate 1 satisfied 0<x<0.5, magnetoresistance effect elementswith a high output voltage value of 0.34 V were obtained.

Examples 31 to 33, Comparative Example 20

An Mg_(1-x1)Al_(x1) alloy film which is expressed by a general formulaMg_(1-x1)Al_(x1) (where x1 has a value described in Table 2) was formedin a thickness of 0.8 nm on the first ferromagnetic layer 2 using asputtering method. Subsequently, the alloy film was oxidized to form anoxide film and a heat treatment was performed thereon to form a firstoxide layer 4 a. The oxidization process was performed by exposing thealloy film to the air under a pressure of 5 Pa for 600 seconds. The heattreatment was performed by heating the oxide film in a vacuum at 400° C.for 15 minutes. Subsequently, an Mg_(1-y)Al_(y) alloy film which isexpressed by a general formula Mg_(1-y)Al_(y) (where y has a valuedescribed in Table 1) was formed in a thickness of 0.8 nm on the firstoxide layer 4 a using a sputtering method, the alloy film was oxidizedto form an oxide film, and a heat treatment was performed thereon toform a second oxide layer 4 b. The conditions of the oxidization processand the heat treatment were set to be the same as in the first oxidelayer 4 a. Subsequently, an Mg_(1-x2)Al_(x2) alloy film which isexpressed by a general formula Mg_(1-x2)Al_(x2) (where x2 has a valuedescribed in Table 2) was formed in a thickness of 0.8 nm on the secondoxide layer 4 b using a sputtering method. Subsequently, the alloy filmwas oxidized to form an oxide film and a heat treatment was performedthereon to form a first oxide layer 4 a. The oxidization process wasperformed by exposing the alloy film to the air under a pressure of 5 Pafor 600 seconds. In this way, a magnetoresistance effect element 20 wasmanufactured in the same way as in Examples 1 to 30 and ComparativeExamples 1 to 19 except that the tunnel barrier layer 4 which is astacked body including the first oxide layer 4 a, the second oxide layer4 b, and the first oxide layer 4 a was stacked on the firstferromagnetic layer 2.

In the manufactured magnetoresistance effect element 20, contentproportions (atomic ratios) of Mg and Al in the first oxide layer 4 aand the second oxide layer 4 b of the tunnel barrier layer were measuredusing the above-mentioned method. As a result, it was ascertained thatthe content proportions of Mg and Al in the first oxide layer 4 a werealmost the same as that in the Mg_(1-y)Al_(y) alloy film or theMg_(1-x2)Al_(x2) alloy film and the content proportions of Mg and Al inthe second oxide layer 4 b were almost the same as that in theMg_(1-y)Al_(y) alloy film. It was also ascertained that both the firstoxide layer 4 a (the oxide film of the Mg_(1-y)Al_(y) alloy film or theMg_(1-x2)Al_(x2) alloy film) and the second oxide layer 4 b (the oxidefilm of the Mg_(1-y)Al_(y) alloy film) had a disordered spinelstructure.

An output voltage value V_(output) of the manufactured magnetoresistanceeffect element 20 was measured as follows. The results are described inTable 2.

TABLE 2 Output First oxide layer Second oxide layer voltage x1 ofMg_(1−x1)Al_(x1) y of Mg_(1−y)Al_(y) First oxide layer value alloy alloyx2 of Mg_(1−x2)Al_(x2) |y − (x1 + x2)/2| (V) Comparative 0.25 0.25 0.250.00 0.20 Example 20 Example 31 0.75 0.25 0.63 0.35 Example 32 0.50 0.150.43 0.35 Example 33 0.75 0.25 0.75 0.50 0.30

From the results described in Table 2, it was ascertained that themagnetoresistance effect elements of Examples 31 to 33 in which thetunnel barrier layer 4 which had an output voltage value a stacked bodyof the first oxide layer 4 a and the second oxide layer 4 b havingdisordered spinel structures with different compositions was higher thanthat of the magnetoresistance effect element of Comparative Example 20.The reason why the output voltage value of the magnetoresistance effectelement of Comparative Example 20 was low is thought to be that thefirst oxide layer 4 a and the second oxide layer 4 b had the samecomposition.

Particularly, the output voltage values of the magnetoresistance effectelements of Examples 31 and 32 were 0.35 V, which is high. The reasonwhy the output voltage values of the magnetoresistance effect elementsof Examples 31 and 32 were high is thought to be that x of the firstoxide layer 4 a satisfied 0<x<0.5 and y of the second oxide layer 4 bsatisfied 0.5<y≤1.

According to the disclosure, it is possible to provide amagnetoresistance effect element with a high output voltage value.

EXPLANATION OF REFERENCES

-   -   10, 20 Magnetoresistance effect element    -   1 Substrate    -   2 First ferromagnetic layer    -   3 Second ferromagnetic layer    -   4, 24 Tunnel barrier layer    -   4 a First oxide layer    -   4 b Second oxide layer    -   30 Magnetoresistance effect device    -   31 First wire    -   32 Second wire    -   33 Electrode    -   34 Power supply    -   35 Voltmeter

What is claimed is:
 1. A magnetoresistance effect element, comprising: afirst ferromagnetic layer; a second ferromagnetic layer; and a tunnelbarrier layer that is interposed between the first ferromagnetic layerand the second ferromagnetic layer, wherein the tunnel barrier layer isa stacked body including one or more first oxide layers and one or moresecond oxide layers with a composition which is different from acomposition of the first oxide layer, at least one of the first oxidelayer or the second oxide layer has a disordered spinel structure, thefirst oxide layer includes an oxide containing a metal or an alloy whichis expressed by General Formula (I),A_(1-x)B_(x)  (I) the second oxide layer includes an oxide containing ametal or an alloy which is expressed by General Formula (II),A_(1-y)B_(y)  (II), and wherein, in General Formula (I) and GeneralFormula (II), A's are independently Mg or Zn, B's are independently atleast one type of metal selected from the group consisting of Al, Ga,and In, and x and y satisfy 0<x≤1, 0<y≤1, and |y−x|≥0.005.
 2. Themagnetoresistance effect element according to claim 1, wherein xsatisfies 0<x<0.5 and y satisfies 0.5<y≤1, or x satisfies 0.5<x≤1 and ysatisfies 0<y<0.5.
 3. The magnetoresistance effect element according toclaim 2, wherein x satisfies 0<x<0.5 and y satisfies 0.5<y≤1.
 4. Themagnetoresistance effect element according to claim 3, wherein the firstferromagnetic layer is formed on a substrate, the first oxide layer isstacked on a surface of the first ferromagnetic layer opposite to thesubstrate, and the second oxide layer is stacked on a surface of thefirst oxide layer opposite to the first ferromagnetic layer.
 5. Themagnetoresistance effect element according to claim 3, wherein thetunnel barrier layer is a stacked body which includes two first oxidelayers and in which the second oxide layer is interposed between the twofirst oxide layers.
 6. The magnetoresistance effect element according toclaim 3, wherein a thickness of the first oxide layer is thinner than athickness of the second oxide layer.
 7. The magnetoresistance effectelement according to claim 1, wherein a thickness of the tunnel barrierlayer is equal to or less than 3 nm.
 8. The magnetoresistance effectelement according to claim 1, wherein both the first oxide layer and thesecond oxide layer have a spinel structure.
 9. The magnetoresistanceeffect element according to claim 1, wherein both the first oxide layerand the second oxide layer have a disordered spinel structure.
 10. Themagnetoresistance effect element according to claim 1, wherein B's areindependently at least one type of metal selected from the groupconsisting of Ga and In.
 11. The magnetoresistance effect elementaccording to claim 1, wherein in General Formula (I), A is Mg or Zn, Bis at least one type of metal selected from the group consisting of Gaand In, and x and y satisfy 0<x≤1, 0<y≤1, and |y−x|≥0.005.
 12. Themagnetoresistance effect element according to claim 1, wherein inGeneral Formula (II), A is Mg or Zn, B is at least one type of metalselected from the group consisting of Ga and In, and x and y satisfy0<x≤1, 0<y≤1, and |y−x|≥0.005.
 13. A method of manufacturing themagnetoresistance effect element according to claim 1 including: a firstferromagnetic layer; a second ferromagnetic layer; and a tunnel barrierlayer that is interposed between the first ferromagnetic layer and thesecond ferromagnetic layer, the tunnel barrier layer being a stackedbody including one or more first oxide layers and one or more secondoxide layers with a composition which is different from a composition ofthe first oxide layer, the method comprising: performing a heattreatment after stacking each of the first and second oxide layers.